CN1452794A - Microporous solid electrolytes and methods for preparing them - Google Patents
Microporous solid electrolytes and methods for preparing them Download PDFInfo
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Abstract
The present invention is directed to an elecrolyte film and/or a solid electrolyte, having a microporous structure, for a rechargeable cell. According to the present invention, when preparing the electrolyte film and/or the solid electrolyte, an inorganic absorbent is added in the amount of more than 70% by weight in a polymer matrix to prevent the porous structure from being destructed at the cell-assembling process such as lamination or pressing, whereby the absorbing power of a liquid electrolyte to the solid electrolyte film and the ionic conductivity can be maintained. The inorganic absorbent contained over the specific amount, together with the microporous structure, improves the capacity of absorbing the liquid electrolyte and, in particular, works as a structure element of increasing the mechanical strength of electrolyte film and/or solid electrolyte.
Description
Technical field
The present invention relates to can be used for the solid electrolyte film of rechargeable battery.More particularly, the present invention relates at rechargeable battery recharge and interdischarge interval is that ion is provided at the path of moving between negative electrode and the anode, this is by introducing liquid component and lithium salts (below, the both is called " liquid electrolyte ") in the solid electrolyte film of the above absorbent of specified quantitative and realize to having multi-cellular structure and comprising.
Rechargeable battery of the present invention comprises three necessary compositions, that is, and and negative electrode, anode and electrolyte.Battery is made by lamination negative electrode, anode and sheet electrolyte.The material that is used for described anode is the polymeric material that carbon maybe can insert/remove lithium metal or lithium ion.The material that is used for described negative electrode is the polymeric material that transition metal oxide maybe can insert/remove lithium metal or lithium ion.Be used for described electrolytical material and can use a kind of electrolyte of the present invention, and liquid electrolyte is introduced wherein after battery assembles again.
Background technology
Battery places between the conductive surface of negative electrode and anode as the electrolyte in rechargeable battery or the electrochemical reaction system.This electrolyte is not have electronic conductivity but the insulator with ionic conductivity.Up to now, general electrolyte only is made up of liquid component; But recently, people more pay close attention to the solid electrolyte with many advantages.Wherein, attempted using polymer to be used as electrolyte.
Has extremely low ionic conductivity 10 because comprise the heteroatomic straight polymer electrolyte of polarity
-8S/cm so they are difficult at room temperature use, therefore, mainly concentrate on the research of polymer dielectric and to improve on its conductivity, and as representational example, the someone advises the liquid electrolyte component is incorporated in the structure of polymer.
At United States Patent (USP) 5,219, the disclosed gel-type electrolyte that comprises liquid electrolyte in polymer backbone has suitable conductivity in 679 when demonstrating polymer property, but, during making polymer dielectric, comprised a large amount of liquid electrolytes, therefore the problem of described patent is that the evaporation/loss of liquid component can take place, and changes thereby cause forming, and conductivity reduces.In addition, because the lithium salts in the liquid electrolyte is very sensitive to moisture, so need very strict dehumidifying condition when making gel electrolyte.
At United States Patent (USP) 5,296,318 and 5,418, what propose in 091 mixes the type polymer electrolyte system, when having the gel-type polymer electrolyte advantage, the influence of moisture to the battery manufacture process can be minimized by add liquid electrolyte after battery packages.Because liquid electrolyte adds after having prepared electrolytic thin-membrane, so, must have the position that can absorb liquid component therein for electrolytic thin-membrane inside.For this reason, in the step of preparation electrolytic thin-membrane, to add plasticizer/processing aid, and after finishing the battery assembling, utilize organic solvent that they are extracted.Yet owing to need this process, so the fatal shortcoming of said method is that reappearance is low, it is low to make yield, is difficult to realize the automation of large-scale production.
In order to address these problems, people attempt forming aperture therein so that can easily absorb liquid electrolyte in the preparation polymer film.More particularly, the someone advises and will dissolved polymers cast form of film in solvent, makes polymer film contact with non-solvent then.Except this method, also the someone proposes by sulfuration, curing or stretches porousness is incorporated in the polymer film.In the time of in liquid electrolyte is absorbed in by the polymer film of method for preparing, their ionic conductivities at room temperature surpass 10
-3S/cm, this numerical value is suitable for commercial Application.But, also there is such problem, that is, porousness is incorporated into process complexity in the polymer, perhaps because the multi-cellular structure that forms in the polymer film takes place to destroy and ionic conductivity is descended rapidly easily in the lamination of assemble or pressing step.In other words, itself demonstrates excellent characteristic polymer dielectric, but it is difficult to be applied to make in the practice of battery.
In order to solve the problem that porousness is destroyed, people attempt directly polymer film being attached on negative electrode and/or the anode, and resulting structures is contacted with non-solvent.But, use electrode surface to make the production process complexity, and have very bad influence for negative electrode and/or anode as the water of non-solvent as the method for preparing the electrolytic thin-membrane substrate.Therefore, it also is difficult to be applied to make in the practice of battery.
United States Patent (USP) 5,631,103 disclose the electrolyte system that wherein adds inorganic filler.But, in order to reach commercial production levels, need to increase the addition of inorganic filler, so the mechanical strength of polymer film can become weak.Therefore, this method also is not suitable for real process.In addition, described patent has been used by adding processing aid therein polymer film has been carried out casting mold, and then is removed so that introduce porous method in film, this method also can cause and is similar to United States Patent (USP) 5,296,318 and 5,418,091 problem.
Meanwhile, Japanese publication communique 99-16561 discloses the polymer electrolyte system that adds inorganic filler in the multi-cellular structure of being made by polyvinylidene fluoride base resin.This system can provide at room temperature good ionic conductivity and can cast the mechanical strength of film shape; But, the content of inorganic material only is the 1.9-66 weight % of electrolytic thin-membrane total amount (being equivalent to per 100 weight portion polyvinylidene fluoride base resin 2-200 weight portions), preferred 4.8-33.3 weight % (being equivalent to the 5-50 weight portion), it is not enough to support multi-cellular structure, thereby causes the short circuit of battery in the destruction of polymer dielectric multi-cellular structure and the battery assembling process.And, because electrolytical in practice ionic conductivity can not maintain constant level, can not produce battery with good characteristic.
Above-mentioned prior art problems may be summarized as follows:
(1) therefore the electrolyte ion electric conductivity difference of being made by straight polymer is difficult to be applied to actual battery manufacture process.
(2) comprising the gel-type polymer electrolyte for preparing under the condition of liquid electrolyte, have at room temperature good ionic conductivity because of the ionic conductivity of liquid electrolyte, but process condition is being restricted, and is difficult to keep the capacity of constant.
(3) by adding plasticizer/processing aid with the preparation film shape, thereby be removed then make liquid electrolyte be absorbed in interior and make mix the type polymer dielectric, its advantage is that described method is not too made condition effect and had sufficient ionic conductivity; But, need complicated a plurality of steps and other material, so the operating cost increase, be difficult to the automation of implementation procedure.
(4) pass through the whole bag of tricks, exchange as solvent/non-solvent, sulfuration, curing, stretching etc. are that multi-cellular structure can destroy in lamination or pressing process, therefore causes the absorption of liquid electrolyte insufficient to the problem of wherein introducing porous polymer dielectric.
(5) but the advantage that forms the method for multi-cellular structure film on electrode surface is that to have increased the adhesive strength process conditions of electrode surface remarkable, so it is not preferred.
(6) someone attempts improving mechanical strength by adding inorganic material, but it can not solve the problem that multi-cellular structure destroys fully in the battery assembling process, nor can keep ionic conductivity.
Simultaneously, the inventor provides a kind of system in PCT 99/KR99/00798, wherein can be by microporosity being incorporated in the electrolyte thin membrane matrix that comprises absorbent so that the absorption of liquid electrolyte is more prone to increase conductivity of lithium ions.In described system,, after the battery assembling, needn't remove described absorbent thus to liquid electrolyte adding after the battery assembling of humidity sensitive.In addition, do not need plasticizer or processing aid in the United States Patent (USP) 5,296,318,5,418,091 and 5,631,103 for example, so technology is simple, the technology cost is low.But as mentioned above, the inventor finds that there is such problem in it, that is, can destroy at the multi-cellular structure with solid electrolyte film in negative electrode and/or anode and the step that film combines, and absorbability can descend.Therefore, the absorbent that the inventor finds need to surpass specified quantitative is so that address the above problem, and finished the present invention thus.
Disclosure of the Invention
Therefore, has the inorganic material of structure filler and absorbent function to prevent the destruction of multi-cellular structure more than the invention provides the adding specified quantitative, and keep the absorbability of solid electrolyte film and in the battery assembling process, as lithium ion conductive in lamination or the compacting.Comprise the above superabsorbent particles of specified quantitative and improved the electrolytical ability of absorption liquid with multi-cellular structure, specifically, as the structural detail that improves electrolytic thin-membrane and/or solid electrolyte mechanical strength.Even after battery assembling, also can keep the good electric conductivity of lithium ion therefore.And, for the absorption of liquid electrolyte, do not need lock out operation, and demonstrate such key character that liquid electrolyte is introducing after the battery assembling.
Solid electrolyte of the present invention comprises inorganic absorbent, also comprises the electrolytic thin-membrane with multi-cellular structure and ionic conductivity liquid electrolyte.In other words, be used for the activation process preparation that the solid electrolyte of rechargeable battery can go by the many micropores electrolytic thin-membrane that the ionic conductivity liquid electrolyte is absorbed only made by inorganic absorbent and polymer adhesive.The term " electrolytic thin-membrane " that is used for this specification is meant and is the electrolytic thin-membrane that drying regime does not comprise any liquid electrolyte.Term " solid electrolyte " meaning that is used for this specification is by introducing the described electrolytic thin-membrane that liquid electrolyte has ionic conductance therein.Although because comprise liquid electrolyte, it is solid-state completely that solid electrolyte is not, and for itself and liquid electrolyte are made a distinction, they is called " solid electrolyte ", because the basic framework of solid electrolyte starts from the solid electrolyte film.
Described electrolytic thin-membrane can preferably be prepared by the inversion of phases method.The example of this method comprises wet method and dry method.Wet method is meant a kind of method that is used to prepare electrolytic thin-membrane, it may further comprise the steps: the mixture of absorbent and polymer adhesive is dissolved in the solvent that is used for polymer adhesive, gained solution is made film like, with the non-solvent exchange solvent that is used for polymer adhesive, dry then gained material is to form electrolytic thin-membrane.On the contrary, dry method is meant the another kind of method that is used to prepare electrolytic thin-membrane, it may further comprise the steps: with the mixture and the solvent that is used for polymer adhesive of absorbent and polymer adhesive, non-solvent, pore-forming agent (pore former) and the wetting agent of dissolve polymer adhesive do not mix, the gained mixture is made film like, then bone dry gained film.
Owing to, be used for the absorbability that inorganic absorbent of the present invention will absorb liquid electrolyte or increase liquid electrolyte, and should not have electron conduction to the high affinity of liquid electrolyte.Equally, they also should have good machinery, heat, chemistry and electrochemical properties.As this inorganic absorbent, can use one or both or the multiple particle that is selected from mineral grain, synthesis oxide compound particle and mesoporous molecular sieve.The example of described mineral grain comprises the mineral grain with phyllosilicate structures, as clay, paragonite, montmorillonite and mica.The example of described synthesis oxide compound particle comprises zeolite, porous silica, Woelm Alumina and magnesium oxide.The example of mesoporous molecular sieve comprises that by oxide the aperture of making as silicon dioxide is the mesoporous molecular sieve of 2-30 nanometer.Described mineral grain, synthesis oxide compound particle and mesoporous molecular sieve can use with the form of mixture, and wherein two or more absorbents that are selected from above-mentioned absorbent combine.
The particle diameter of inorganic absorbent preferably is no more than 40um, more preferably no more than 20um, so that do not reduce the mechanical strength and the uniformity of electrolytic thin-membrane.But, when particle diameter too hour, absorbability descends or the electrolytic thin-membrane made has the tendency of compact structure, so it is not preferred.Prior art has been used very little (for example, the being lower than 20nm) inorganic material of particle diameter as Japanese publication communique 1999-16561; But in this case, inorganic material can not be used as absorbent, the crystallinity that may hinder filler or polymer film on the contrary.That is, in order to show absorbent and structural detail characteristic together, inorganic absorbent should have the above particle diameter of 50nm or in the aggregated forms of several microns units among the present invention.Form to inorganic absorbent has no particular limits, and it can be fiber, pin, plate or spherical, but preferred asymmetrical form is so that increase the mechanical strength of electrolytic thin-membrane.
First purpose of the present invention is to prepare the solid electrolyte that keeps liquid electrolyte absorbability and ionic conductivity, and it is destroyed and even also have a fact of mechanical strength after the battery assembling that it comes from multi-cellular structure.The inventor finds that the amount of inorganic absorbent is to realize the key condition of above-mentioned purpose.More than at least 70 weight % of the electrolytic thin-membrane amount that the amount of inorganic absorbent preferably is made up of inorganic absorbent and polymer adhesive, more preferably 70%-95 weight %.When it during greater than 95 weight %, ionic conductivity does not increase along with the increase of amount, on the contrary, the mechanical strength of formed electrolytic thin-membrane and the surface adhesion between the electrode can deteriorations.On the contrary, 70 weight % are the starting points that exist in down problem.
At first, when the amount of inorganic matter is no more than 70 weight %, because the multi-cellular structure of solid electrolyte film tends to destroy in the lamination of battery assembling or pressing step, so the absorbability of liquid electrolyte and ionic conductivity can reduce greatly.The inventor has prepared the solid electrolyte film that contains different amount inorganic absorbent, observes the variation that thickness and ionic conductance take place with the external pressure that applies in the battery production process then.Thickness and the ionic conductance of finding solid electrolyte film from such test change suddenly since 70 weight %.Do not have hint in the prior art or instructed such situation, this is that the inventor finds first.Based on experimental fact, have only the 70 weight % of surpassing to guarantee that battery has good performance, wherein the multi-cellular structure of solid electrolyte can not destroyed by the external pressure that production process applies, this content can not reduce the electrolytical ability of liquid that absorbs yet, and has therefore kept ionic conductance.
Secondly, when the amount of inorganic matter is no more than 70 weight %, because come the volume parts of said polymer big, so the distortion of shape becomes greatly with respect to the total weight of solid electrolyte.That is, because can shrink/swelling, so the dimensional stability of electrolytic thin-membrane/solid electrolyte descends in the electrolytical step of drying or when battery assembles the electrolytical step of back steeping liq.
The 3rd, when the inorganic matter amount is no more than 70 weight %,, also be difficult to solve fully the problem that electrolyte occurred that mainly comprises polymer even comprise many absorbents.For example, as in existing polymer dielectric, under low temperature or high temperature deterioration can take place.Usually, because the ionic conductivity in the direct impact polymer electrolyte of the motion of polymer chain, so temperature becomes very remarkable to the influence of ionic conductivity.Particularly, the motion of polymer chain is restricted at low temperatures, and it can reduce ionic conductivity significantly, therefore causes battery performance that serious deterioration takes place.On the other hand, as in the present invention, use inorganic absorbent can increase ionic conductivity.In addition, use the not thermally sensitive inorganic absorbent that surpasses specified quantitative, can be dropping to minimum with the incompatible temperature effect of polymer dielectric that exists.Equally because include a large amount of inorganic absorbent in the electrolyte, so electrolyte of the present invention has such advantage, it is anti-ignite or the blast ability with comprise a large amount of organic materials, compare as the electrolyte of polymer and be improved.
The addition of considering inorganic substances in prior art or other correlation technique is generally about 50 weight % or lower, therefore such discovery, having only the discovery that just can address the above problem when the organic absorbent that comprises surpasses specific amount is outside the non-common practice to existing universal, and it is to finish by many experiment and analyses based on a large amount of adding inorganic substances.
As polymer adhesive, can use the most general polymer.Wherein, preferred one or both or multiple following listed mixture of polymers, polyvinylidene fluoride, the copolymer of vinylidene fluoride and hexafluoropropylene of being selected from of using, the copolymer of vinylidene fluoride and maleic anhydride, polyvinyl chloride, polyvinyl alcohol, polyvinyl formal, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethane, polyimides, Merlon, polysulfones, polyethers, poly(ethylene oxide), polyolefin such as polyethylene or polypropylene, polyisobutene, polybutadiene, polyacrylonitrile, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethylene glycol) diacrylate, dimethione and polysilicon, or its copolymer or polymeric blends.
Not preferably in heating with add and depress the polymer adhesive that character changes on a large scale or cross-linking reaction, curing reaction etc. take place.Equally, also preferably when free state by adding the polymer adhesive of at least a material with regard to induced polymerization, copolymerization, crosslinked, curing reaction.This is because unreacted monomer may be immersed in the inorganic absorbent, and its can be with electrolyte compound react and reduce the performance of battery subsequently, therefore needs separation process that they are removed.Therefore, preferably avoid in the assembling process of the manufacture process of electrolytic thin-membrane or battery, may taking place the situation of the problems referred to above.
As the solvent that is used for polymer adhesive, it has dissolubility to polymer adhesive, can use a kind of, two or more are selected from the mixture of following solvent: the N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane.
As the non-solvent that is used for polymer adhesive, it does not have dissolubility or has very little dissolubility polymer adhesive, and it can be miscible with solvent, can use one or both or multiplely be selected from following mixture: water, ethanol, ethylene glycol, glycerine, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
Below, will explain described method for preparing solid electrolyte in more detail with loose structure.
Wet method
Solid electrolyte with multi-cellular structure of the present invention can be prepared by the wet method of being made up of five steps, that is, the dissolve polymer adhesive mixes inorganic absorbent, plastic casting film, preparation porous polymer matrix and drying, and activation.
At first, polymer adhesive is dissolved in the solvent, in solution, adds inorganic absorbent then, fully mix so that it is uniformly dispersed.The solid content of described mixed solution is preferably the 5-60 weight % of total solution weight.If content is no more than 5 weight %, the mechanical strength of electrolytic thin-membrane reduces, if content greater than 60 weight %, inorganic absorbent can not fully be disperseed or the viscosity of mixed solution can become very high, this can have problems.
For the ease of the dispersion of inorganic absorbent, can use magnetic stirring apparatus, mechanical agitator, planet strrier or high speed dispersion device to stir mixed solution.When stirring, can adopt the ultrasonic agitation device to prevent absorbent aggegation during mixing or foaming.In addition, if desired, mixed solution can carry out froth breaking and filtration step.
After even mixed polymer adhesive and inorganic absorbent, the mixture that obtains is made form of film.For example, mixed solution can be poured on the flat board, carry out casting mold then.Perhaps, can mixed solution be extracted from punch die, be coated onto on the substrate then with fixing slit.As substrate, can use the material that has chemistry, heat and mechanical stability and can during lamination process, separate with electrolytic thin-membrane, for example, can use polymer film, as polyester, polytetrafluoroethylene, paper etc.Can select various other coating processes.
Behind casting mold, film is contacted the solvent that is used for polymer adhesive with exchange with non-solvent.For example, can be by film being immersed in the non-solvent pond and solvent extraction is come out.Therefore, preferably select the combination of miscible solvent and non-solvent.Different according to solvent and non-solvent type, the soak time in the non-solvent pond changed from one minute to one hour.When the time more in short-term, be difficult to obtain sufficient porousness.On the contrary, surpass the time that is limited when the time, the productivity ratio step-down, this is not preferred.Temperature in the pond is preferably 10 ℃-90 ℃, more preferably 20 ℃-80 ℃.If temperature is lower than said temperature, be difficult to obtain sufficient porousness, if temperature is too high, the mechanical strength of electrolytic thin-membrane reduces, this neither be preferred.After extractant and bone dry gained film, make electrolytic thin-membrane.
Dry method
Solid electrolyte with multi-cellular structure of the present invention can be prepared by the dry method of being made up of five steps, that is, and and the dissolve polymer adhesive, mix inorganic absorbent, add additive (non-solvent, pore-forming agent, wetting agent), plastic casting film and drying, and activation.
Polymer adhesive is dissolved in the solvent, in solution, adds inorganic absorbent then, fully mix so that it is uniformly dispersed.Dispersion or blend step are the same with wet method.After even mixed polymer adhesive and absorbent, add the non-solvent that consumption can not cause the polymer adhesive precipitation.For the ease of forming multi-cellular structure, preferably add pore-forming agent or wetting agent.The film casting step is the same with wet method.After finishing film preparation, the electrolytic thin-membrane that obtains at 20 ℃ of-200 ℃ of following bone dries to make electrolytic thin-membrane.
Compare with wet method, dry method has following shortcoming, therefore more preferably uses wet method.
(1) under the dry method situation, relatively is difficult to disperse fully or composite absorber, polymer adhesive and additive.When disperseing or mixing and carry out when incomplete, (i) be difficult to realize the even dispersion of pore-forming agent or absorbent, (ii) be difficult for casting mold and become the form of electrolytic thin-membrane and (iii) mechanical strength and reappearance step-down.That is, disperse to confirm already under the uneven situation that (a) when electrolytic thin-membrane was used as the electrolyte of electrochemical cell, the reaction in the battery was carried out with non-homogeneous localized state at pore-forming agent or absorbent; (b) casting mold with form of film becomes difficult; (c) mechanical strength reduces, and this can cause serious restriction to dry method.
(2) in order to form the hole, dry method need add non-solvent, considers the principle of dry method, and solvent should be prior to the non-solvent evaporation so that can form the hole.If non-solvent prior to solvent evaporation, just can not form the hole.In this respect, non-solvent should have fixedness or have the boiling point higher than solvent and is absolutely necessary.For this reason, there is the problem of residual non-solvent probably in dry method.In other words, non-solvent, it has than the higher boiling point of solvent or for nonvolatile, is difficult to remove from electrolytic thin-membrane fully in drying steps.Therefore, should take another step (for example, with the extraction of alcohol or ether or fully increase baking temperature) in order to remove non-solvent fully.In addition, because described non-solvent is at chemistry with in instability aspect the electrochemistry, if described non-solvent is stayed in the electrolytic thin-membrane, it may cause side reaction or by the recharge of battery and discharge institute's oxidation or reduction, therefore, degradation of cell performance may take place, and reduces or the gas effusion as battery capacity.Identical problem is applicable to other additives except that non-solvent.It is believed that to wait the method that only prepares the electrolytic thin-membrane of being made up of absorbent and polymer adhesive may be complicated by removing additive fully, it makes this method be difficult to carry out repetition.
Preferably with the THICKNESS CONTROL of film of the present invention in the 20-200um scope.If film thickness is no more than 20um, mechanical strength reduces, so it is not preferred.On the contrary, if film thickness surpasses 200um, ionic conductance reduces, so it neither be preferred.The aperture of preferred electrolytic thin-membrane of the present invention is lower than 20um, more preferably less than 10um, and 0.01-5um more preferably in addition.The porousness of preferred electrolytic thin-membrane of the present invention is 5-95%, more preferably 20-90%, more preferably 40-85% in addition.
The liquid electrolyte that absorbs in the microporous film that as above prepares can be prepared by lithium salts is dissolved in the organic solvent.
Preferred described organic solvent has high polarity, and does not react with lithium metal so that improve the degree of dissociation of ion and promote ionic conductivity by reducing ion local viscosity on every side by improving electrolytical polarity.Such representative examples of organic comprises ethylene carbonate (EC), propylene carbonate (PC), carbonic acid fourth diester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene methyl esters (EMC), r-butyrolactone (GBL), methyl-sulfoxide (DMSO), 1,3-dioxane (DO), oxolane (THF), 2-methyltetrahydrofuran, sulfolane, N, dinethylformamide (DMF), diethylene glycol dimethyl ether (DME), triglyme and tetraethylene glycol dimethyl ether.Particularly, the preferred organic solvent that uses is the form of the mixed solution of two or more solvents, is made up of high viscosity solvent and low viscosity solvent.
Described lithium salts preferably has the low lattice energy and the high degree of dissociation.The example of this lithium salts comprises LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiSCN, LiCF
3SO
3, LiN (CF
3SO
2)
2And LiC (CF
3SO
2)
3Also can use its optionally mixture.The concentration of lithium salts is preferably 0.5M-2M.
The addition of liquid electrolyte can be the 20-90 weight % of the electrolyte total amount that contains liquid electrolyte, preferred 40-85 weight %.In this case, the conductivity at room temperature of the lithium ion in the solid electrolyte is 1-3mS/cm.
The object of the present invention is to provide chargeable battery, particularly rechargeable lithium battary, wherein said many microporous solids electrolyte is as electrolyte.
The method that preparation the present invention contains the rechargeable battery of solid electrolyte is described below.
The electrolytic thin-membrane that passes through above-mentioned steps preparation of negative electrode and anode and insertion combined with modes such as lamination, compactings realize the assembling of battery.Negative electrode and anode are prepared respectively, and cathodic electricity is connected on the cathode current collector, and anode is electrically connected on the anode current current-collector.Thus, the device that assembles is activated so that it can absorb liquid electrolyte, obtain the electrochemical cell that to operate at any time thus.
Preferably prepare electrolytic thin-membrane and electrode (negative electrode and anode) respectively, because like this, quality control, technological design and equipment are all fairly simple.In case of necessity, in order to increase the binding ability between electrode and the electrolytic thin-membrane and to make that the thickness of electrolytic thin-membrane is thinner, can directly coat on the electrode to form electrolytic thin-membrane by the solid electrolyte slurries that absorbent, polymer adhesive, solvent etc. are formed.But said method is not preferred, because do not match each other when electrode and electrolytic thin-membrane, or when electrode or electrolytic thin-membrane is contaminated easily or in manufacture process easily during its performance of forfeiture, this method will be difficult to employing.
Consider the performance or the process condition of battery, for electrolytic thin-membrane is placed between the electrode, the method for assembling or being laminated on the battery by lamination or pressing mode can be improved then.(i) at first electrolytic thin-membrane is laminated on the electrode in negative electrode and the anode, another polar stack is to the another side of electrolytic thin-membrane then.(ii) electrolytic thin-membrane is laminated to respectively on the surface of negative electrode and anode, then with the right state of electrolyte face with negative electrode and anode lamination.(iii) negative electrode, electrolyte and anode lamination in turn simultaneously.
In lamination process, the feasible reduction with electrolytic thin-membrane of the lamination condition of preferred settings minimizes, and makes it be no more than 50 volume %.The volume of electrolytic thin-membrane reduces the destruction that means loose structure, but for carrying out lamination by heating or compacting, it is inevitable that the volume of a little reduces.Therefore, find that volume can be reduced minimized lamination condition be useful.As mentioned above, confirmed already that the inorganic absorbent of adding surpassed at least 70 weight %, this is a most important characteristic of the present invention, this volume can be reduced to minimize.
If desired, for the volume of limit electrolysis matter reduces, can use certain method to be set at temperature and pressure low as far as possible and make the combination between electrode and the electrolytic thin-membrane be undertaken by tack coat.For example, can use the PE solution, ethylene/ethyl acrylate base or Ethylene/vinyl acetate based adhesive etc.But these adhesive components should have heat, chemistry and electrochemical stability, and the loose structure that the tack coat of being made by them should deface and do not increase the damping on surface.Therefore, consider the manufacturing and the Properties Control of battery, preferably use tack coat.
The method that is used to prepare negative electrode or anode is as follows.Negative electrode or anode are made up of current-collector and active material layer.Active material layer comprises active material, conductive materials and adhesive etc.In addition, can introduce various additives for the performance that improves battery.According to desired purpose, the current-collector, conductive materials, adhesive and the additive that are included in negative electrode or the anode can be identical or different.The mixture of each negative electrode or anode material is kneaded and is obtained slurries together.The slurries that obtain are made into film by casting mold, coating and silk screen printing, by compacting or lamination the film that obtains are combined with current-collector then and form negative electrode and/or anode.Perhaps, slurries directly can be coated on the current-collector to form negative electrode and/or anode.
The path that current-collector provides electronics to move, described electronics are to produce in the oxidation/reduction reaction of negative electrode or anode generation.As current-collector, according to the performance and the manufacture process of battery, can use screen usually, paper tinsel, punching paper tinsel and etched foil etc.The use screen can increase the load of active material, but it may make production process complicated.Use paper tinsel can improve the performance of battery and simplify manufacture process, but it may make the compactness deterioration of active material.Copper, aluminium, nickel, titanium, stainless steel, carbon etc. all can be used as current-collector.Usually, aluminium is used for negative electrode, and copper is used for anode.If desired, can carry out preliminary treatment to current-collector, as washing, surface treatment or tack coat apply.
In view of the charging and the exoelectrical reaction (or oxidation/reduction reaction) of battery occurs in this fact on the active material, it is believed that active material is the most conclusive component of electrochemical cell, because it has determined the performance of battery.In addition, active material occupies maximum level in active material layer.As cathode active material, can use transition metal oxide/sulfide, organic compound, polymer etc. preferably can use metal oxide or polymer, as cobalt-lithium oxide (Li
xCoO
2), nickel oxide lithium (Li
xNiO
2), nickel cobalt lithium oxide (Li
xNi
yCo
1-yO
2), spinel-type manganese oxide lithium (Li
xMn
2O
4), manganese dioxide (MnO
2) etc.As anode active material, can use alkali metal, alkaline-earth metal, carbon, the oxide of transition metal or sulfide compound, organic compound and polymer preferably can use carbon or polymer.Importantly should select active material according to the battery performance or the purposes of hope.
Conductive materials refers in order to improve electron conduction and joins material in negative electrode or the anode, normally carbon.Wherein, the preferred graphite of conductive materials, coke, activated carbon and carbon black, more preferably graphite and carbon black.Can use one or both or multiplely be selected from above conductive materials, they are artificial or crude, and are as broad as long.The addition of conductive materials is the 3-15 weight % of electrode material total weight.If the amount of the conductive materials that adds is no more than 3 weight %, electrical conductance descends, thereby causes superpotential problem.If consumption surpasses 15 weight %, the energy density of unit volume reduces, and it is serious that the side reaction that conductive materials causes becomes.
Adhesive refers to adding to increase the component of active material binding ability, normally polymer.The polymer that is used to prepare solid electrolyte film can be used as adhesive.Preferred use with the polymer phase of electrolytic thin-membrane with or have an adhesive of miscibility.The addition of adhesive is 15 weight % of electrode material total weight or still less.If the amount of adhesive is lower than required consumption, the binding ability of electrode may reduce.If the amount of adhesive surpasses 15 weight %, the processability of electrode and porousness reduce.
Additive refers to adding to improve the material of battery or electrode performance, can select in very wide scope according to the performance or the purposes of hope.Add additive and be in order to improve the binding ability with combination electrode inside or current-collector, make combination electrode produce porousness or amorphism, improve to constitute material dispersed of combination electrode or be used to make the efficient of the method for electrode, stop overcharging/over-discharge of active material, again in conjunction with or remove the side reaction thing, or improve the absorbability of liquid electrolyte.Usually, can use salt, organic/inorganic compound, mineral and polymer, can select the absorbent that joins in the electrolytic thin-membrane as additive.
In a word, compared with prior art, the rechargeable battery of solid electrolyte of the present invention and the described solid electrolyte of use has the following advantages:
(1) manufacture process and material requirements are simple.The formation of film is simple, by straightforward procedure, can obtain good porousness as wet method; Therefore, with prior art, that is, sulfuration, curing drawing process particularly use the method for plasticizer/processing aid to compare, and it is very simple.In addition, electrolytic thin-membrane of the present invention has simple composition, and it comprises a large amount of inorganic absorbent and a spot of polymer adhesive, does not need plasticizer/processing aid separately, cure polymer, cross-linked polymer or fibre structure material.
(2) electrolytical performance and excellent in stability.Because the conduction of ion is undertaken by the liquid phase that impregnated in the loose structure, so the ionic conductivity height.Polymer content is low, inorganic absorbent content height, and (i) ionic conductivity is not subjected to Temperature Influence thus, and (ii) mechanical, thermal and electrochemical excellent in stability and (iii) little because of change in volume is so dimensional stability is good.In addition, electrolyte of the present invention has broad electrochemical potential window (potential window) and anti-igniting and the blast ability.Particularly, comprise the above inorganic absorbent of specified quantitative as structural detail, it has improved the damping in lamination or the pressing process, and the reduction of electrolyte performance also seldom therefore even after the battery assembling.
(3) assembling of battery is simple.During preparation electrolytic thin-membrane and assemble, do not need the specific wet atmosphere of removing; Therefore, manufacture process is simple, the automation of easy realization of large-scale production.
The accompanying drawing summary
Fig. 1 illustrates the result of the test figure that shows the linear sweep voltammetry of measuring solid electrolyte electrochemical stability of the present invention.
Fig. 2,4 and 5 discharge capabilities that the battery that has used inorganic absorbent of the present invention is shown change.
Fig. 3 illustrates with the thickness of the film of different content inorganic absorbent preparation and the variation of ionic conductivity, wherein changes and uses with respect to representing with the comparative result of initial value.
Implement best mode of the present invention
In the present invention, describe solid electrolyte of the present invention and in detail by using described solid electrolyte to prepare the method for battery.The preparation and the performance test of solid electrolyte have been carried out.In addition, with solid electrolyte and anode and the negative electrode formation battery that is assembled together, the program that detects battery performance has been described then.But the present invention is not limited to those embodiment, can carry out various changes to it within the scope of the invention.Embodiment 1 (wet method: the experiment of carrying out according to the kind of the kind of inorganic absorbent and consumption and liquid electrolyte)
14g PVdF (polyvinylidene fluoride) is dissolved in preparation polymer binder solution among the 86g NMP (N-methyl pyrrolidone).Add inorganic absorbent in this solution, continuous stirring is disperseed fully up to inorganic absorbent then.In order to stop absorbent granules aggegation each other, when stirring, solution was carried out ultrasonic stirring 30 minutes.The mixed solution of preparation like this is applied on the glass plate that thickness is 100um.To film be immersed in non-solvent bathe in about 10 minutes, from bathe, shift out then and 70 ℃ dry 1 hour down.The porous electrolyte film of preparation like this was immersed in the liquid electrolyte solution about 10 minutes.After liquid electrolyte was absorbed fully, gravimetry changed.Also by utilizing alternating current impedance method to measure ionic conductivity.
Table 1 has been summarized the kind of inorganic absorbent and adhesive, and the content of porous solid electrolyte and the character of conductivity aspect.Absorb the electrolytical ability of liquid, absorbability (Δ in order to compare the porous electrolytic thin-membrane
Ab) be defined as follows:
Δ
Ab=[amount of the liquid electrolyte of absorption (milligram)]/[weight of electrolytic thin-membrane (milligram)]
In addition, the situation meaning of not pointing out to contain the solvent volume of liquid electrolyte refers to that solvent is with identical volume mixture.
Table 1
| Embodiment | Absorbent | ???PVdF | Absorbed dose (%) | Non-solvent | Liquid electrolyte | ???Δ ab | Ionic conductivity (mS/cm) | Mechanical strength | |
| Kind | ????g | ????g | |||||||
| ????a | Paragonite | ?0.18 | ?0.60 | ??23.1 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????7.2 | ?????1.8 | Good |
| ????b | Paragonite | ?0.17 | ?0.31 | ??35.4 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????6.9 | ?????2.1 | Good |
| ????c | Paragonite | ?0.31 | ?0.28 | ??52.5 | ????H 2O | ????EC/PC ?????1M ????LiPF 6 | ????6.7 | ?????1.9 | Good |
| ????d | Paragonite | ?0.72 | ?0.24 | ??75.0 | ????H 2O | ????EC/PC ?????1M ????LiPF 6 | ????6.9 | ?????1.9 | Good |
| ????e | Paragonite | ?1.06 | ?0.26 | ??80.3 | ????H 2O | ????EC/PC ?????1M ????LiPF 6 | ????7.5 | ?????1.8 | Good |
| ????f | Paragonite | ?0.85 | ?0.26 | ??76.6 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????7.9 | ?????2.1 | Good |
| ????g | Paragonite | ?1.51 | ?0.26 | ??85.3 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????8.0 | ?????2.4 | Good |
| ????h | Paragonite | ?2.00 | ?0.26 | ??88.5 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????8.5 | ?????2.5 | Good |
| ????i | Paragonite | ?1.98 | ?0.25 | ??88.8 | Ethanol | ????EC/DMC ?????1M ????LiPF 6 | ????5.1 | ?????1.0 | Good |
| ????j | Zeolite | ?1.37 | ?0.60 | ??69.5 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????7.2 | ?????1.9 | Good |
| ????k | Zeolite | ?1.50 | ?0.38 | ??79.8 | ????H 2O | ????EC/DMC ?????1M ????LiPF 6 | ????8.2 | ?????2.0 | Good |
| ????l | Zeolite | ?1.65 | ?0.29 | ??85.1 | ????H 2O | ?????EC/DMC ??????1M ?????LiPF 6 | ????8.0 | ?????2.4 | Good |
| ????m | Montmorillonite | ?1.34 | ?0.58 | ??69.8 | ????H 2O | ?????EC/DMC ??????1M ?????LiPF 6 | ????8.0 | ?????2.8 | Good |
| ????n | Montmorillonite | ?1.50 | ?0.38 | ??79.8 | ????H 2O | ?????EC/DMC ??????1M ?????LiPF 6 | ????8.2 | ?????2.9 | Good |
| ????o | Porous silica | ?1.35 | ?0.59 | ??69.6 | ????H 2O | ?????EC/DMC ??????1M ?????LiPF 6 | ????8.5 | ?????2.4 | Good |
In above table 1 and following table 2, project " mechanical strength " is when forming electrolytic thin-membrane or measure under the electrolytical state of steeping liq, so it is different with meaning that electrolytic thin-membrane demonstrates when battery assembles anti-lamination of energy or compacting.That is to say in table, to have a kind of content difference of good mechanical strength, when battery assembles, may demonstrate different character according to inorganic absorbent.Embodiment 2 (wet method: the experiment of carrying out according to adhesive type)
Experimentize by changing adhesive type in similarly to Example 1 mode, the result is summarized in table 2.
Table 2
Embodiment 3 (dry method)
| Embodiment | Absorbent (paragonite) | Adhesive | Absorbed dose (%) | Liquid electrolyte | ????Δ ab | Ionic conductivity (mS/cm) | Mechanical strength | |
| ????g | Material | ???g | ||||||
| ????p | ????1.98 | ??PVdF | ??0.24 | ??89.2 | ???EC/DMC ?????1M ????LiPF 6 | ????8.1 | ?????2.4 | Good |
| ????q | ????2.00 | ?P(VdF ?-HFP) | ??0.26 | ??88.5 | ???EC/DMC ?????1M ????LiPF 6 | ????8.0 | ?????2.6 | Good |
| ????r | ????1.95 | ??PAN | ??0.25 | ??88.6 | ???EC/DMC ?????1M ????LiPF 6 | ????7.8 | ?????2.2 | Good |
| ????s | ????2.00 | ???PU | ??0.26 | ??88.5 | ???EC/DMC ?????1M ????LiPF 6 | ????8.9 | ?????2.9 | Good |
| ????t | ????1.98 | ??PVC | ??0.25 | ??88.8 | ???EC/DMC ?????1M ????LiPF 6 | ????7.4 | ?????2.0 | Good |
0.5g P (VdF-HFP) (poly-(vinylidene fluoride-hexafluoropropylene)) is dissolved in place the 20ml phial 8g acetone with the preparation polymer binder solution.Add the 1.17g paragonite in the gained mixture, continuous stirring is disperseed fully up to particle then.In order to stop absorbent granules aggegation each other, when stirring, gained solution was carried out ultrasonic stirring 30 minutes in addition.In the gained mixed solution, add 0.9g ethylene glycol, 0.1g Triton X-100 (wetting agent) and 1.8g isopropyl alcohol (pore-forming agent), then the gained mixture is carried out about 10 minutes mixtures up to adding of ultrasonic stirring and evenly mixed.The mixed solution of preparation like this is applied on the glass plate that thickness is 100um.Film about 2 hours of 40 ℃ of dryings in being set at 50 ℃ vacuum desiccator dry about 6 hours in addition.The electrolytic thin-membrane of preparation like this is dipped in EC/DEC 1M LiPF
6In the solution about 10 minutes.After liquid electrolyte was absorbed fully, gravimetry changed.Δ by weight change determination
AbValue is 7.5.At room temperature the conductivity of measuring by alternating current impedance method is 2.0mS/cm.Embodiment 4 (comparative example: preparation has the experiment of the solid electrolyte of non-porous structure)
14g PVdF is dissolved among the 86g NMP with the preparation polymer binder solution.2g paragonite powder joins in the 1.85g polymer binder solution, and continuous stirring is mixed fully up to particle then.In order to stop absorbent granules aggegation each other, when stirring, gained solution was carried out ultrasonic stirring 30 minutes in addition.The mixed solution of preparation like this is applied on the glass plate that thickness is 100um.Filmed at room temperature dry about 2 hours, and be controlled in about 50 ℃ vacuum desiccator dry about 6 hours in addition in temperature then.The electrolytic thin-membrane of preparation like this is dipped in EC/DEC 1M LiPF
6In the solution about 10 minutes.After liquid electrolyte was absorbed fully, gravimetry changed, and utilized alternating current impedance method to measure conductivity.The lithium ion electric diversion of measuring at room temperature is 0.72mS/cm.The difference of this embodiment and embodiment 1-3 is not implement to form the method for loose structure.Can confirm that from the result of this embodiment introducing porous method in wet method or dry method is essential for the performance of improving battery.Embodiment 5 (electrochemical stability experiment)
In order to measure many microporous solids electrolyte electrochemical stability, by utilizing stainless steel (#304) as work electrode, lithium metal carries out linear sweep voltammetry mensuration as counterelectrode and reference electrode.The electrochemical voltage that applies in linear sweep voltammetry is from the open circuit voltage to 5.5V, and the sweep speed of linear sweep voltammetry is 10mV/ second.Among Fig. 1, setting-out line scanning voltammetry result represents with A, B, C and D respectively on many microporous solids electrolyte that the method by embodiment 1-(h), 1-(1), 1-(n) and 2-(s) prepares, as can be seen from Figure 1, still stable according to solid electrolyte of the present invention its electrochemistry aspect when the 4.8V.Can find out that equally, also the synthesis oxide absorbent is more stable than natural minerals absorbent.Embodiment 6 (battery performance experiment)
In order to measure the performance of the battery that has used solid electrolyte, by preparation battery as follows.By with oxide active material, conductive carbon powder, polymer adhesive and additive with 82: 7: 8: 3 weight ratio is mixed mutually with slurries, and slurries are coated on the alum gate plate, is dried then to prepare negative electrode.By with Delanium, conductive carbon powder, polymer adhesive and additive with 85: 3: 10: 2 weight ratio is mixed mutually with slurries, and slurries are coated on the copper screen, is dried then to prepare anode.Negative electrode, electrolytic thin-membrane and three (3) layers of while of anode lamination are prepared battery, make battery absorb liquid electrolyte then.Use the packing film sealed cell, except electrode end is exposed.On the battery of making like this, charge and discharge test.Apply constant current with the speed (C/2 speed) that is charged to reversible capacity in 2 hours, become 4.2V up to cell voltage, and then apply the constant voltage of 4.2V, be reduced to the C/10 milliampere up to electric current.Subsequently, apply discharging current in 2 hours, to discharge into the speed that voltage is 2.5V or 2.75V (C/2 speed).Recharge and discharge test are measured the variation that discharge capacity takes place with charging and discharge.Battery is formed and result of the test is summarized in following table 3 and be shown in Fig. 2.Listed as table 3, solid electrolyte refers to liquid electrolyte wherein and is absorbed into situation in the electrolytic thin-membrane.In addition, the solid electrolyte that obtains among the embodiment 4 is not carried out battery testing.
Table 3
| Embodiment | Negative electrode | Anode | Solid electrolyte | Figure | ||||||
| Active material | Conductive materials | Adhesive | Additive | Active material | Conductive materials | Adhesive | Additive | |||
| ????u | ??LiCoO 2 | Carbon black | ???PVdF | Paragonite | Graphite | Carbon black | ????PVdF | Paragonite | Embodiment 1-(g) | Fig. 2-E |
| ????v | ??LiCoO 2 | Carbon black | ???PVdF | Zeolite | Graphite | Carbon black | ????PVdF | Zeolite | Embodiment 1-(1) | Fig. 2-F |
| ????w | ??LiCoO 2 | Carbon black | ?P(VdF-HFP) | Zeolite | Graphite | Carbon black | ?P(VdF-HFP) | Zeolite | Embodiment 3 | Fig. 2-G |
| ????x | ??LiMn 2O 4 | Carbon black | ?P(VdF-HFP) | Paragonite | Graphite | Carbon black | ?P(VdF-HFP) | Paragonite | Embodiment 2-(q) | Fig. 2-H |
Fig. 2 shows the battery that obtains by respective embodiments and carries out the discharge capacity in recharge and when discharge and the comparison of discharge capacity for the first time.Confirm from result of the test, use the battery (embodiment 6-w) of the solid electrolyte that obtains by dry method (embodiment 3) to compare with those, solid electrolyte (the embodiment 6-u that uses wet method (embodiment 1 and 2) to obtain, v, x) demonstrate much better battery performance, promptly, comprise inorganic absorbent and have much better influence for the total performance of battery (charging and discharge performance etc.) by the solid electrolyte that wet method prepares, although the character of electrolytic thin-membrane or solid electrolyte itself (ionic conductivity, mechanical strength etc.) does not demonstrate any marked difference.Embodiment 7 (according to the property experiment that carries out as the variation of the paragonite amount of inorganic absorbent)
By changing the amount of the same paragonite powder as inorganic absorbent with embodiment 1, then under 130 ℃, in 15 seconds, forcing press is suppressed with 1 ton pressure and is prepared 10cm by experiment
2The porous solid electrolyte film.The variation of thickness between before and after the mensuration compacting also uses alternating current impedance method to measure the variation of compacting front and back ionic conductivity, and the result is summarized in table 4.Fig. 3 expresses compacting rear film thickness and ionic conductivity is expressed as based on the film thickness before the compacting and the percentage of ionic conductivity.The liquid electrolyte that uses when measuring ionic conductivity is EC/DMC/DEC 1M LiPF
6
Table 4
| Embodiment | Absorbent | ????????PVdF | Absorbed dose (%) | Before the compacting | After the compacting | |||
| Kind | ????g | ????g | Film thickness (μ m) | Ionic conductivity (mS/cm) | Film thickness (μ m) | Ionic conductivity (mS/cm) | ||
| ????y | Paragonite | ??0.18 | ??0.60 | ??23.1 | ????100 | ????1.7 | ????30 | ????0.10 |
| ????z | Paragonite | ??0.17 | ??0.31 | ??35.4 | ????100 | ????2.0 | ????35 | ????0.15 |
| ????aa | Paragonite | ??0.31 | ??0.28 | ??52.5 | ????100 | ????1.8 | ????40 | ????0.25 |
| ????bb | Paragonite | ??0.46 | ??0.27 | ??63.0 | ????100 | ????1.9 | ????45 | ????0.35 |
| ????cc | Paragonite | ??0.57 | ??0.24 | ??70.4 | ????100 | ????2.0 | ????50 | ????0.50 |
| ????dd | Paragonite | ??0.73 | ??0.25 | ??74.5 | ????100 | ????2.0 | ????60 | ????0.8 |
| ????ee | Paragonite | ??1.06 | ??0.26 | ??80.3 | ????100 | ????2.1 | ????80 | ????1.2 |
| ????ff | Paragonite | ??1.98 | ??0.26 | ??88.4 | ????100 | ????2.5 | ????85 | ????1.8 |
| ????gg | Paragonite | ??3.65 | ??0.20 | ??94.5 | ????100 | ????2.6 | ????90 | ????2.0 |
| ????hh | Paragonite | ??5.02 | ??0.15 | ??97.1 | ????100 | ????2.7 | ????90 | ????2.1 |
Confirm by top result, when the content of inorganic absorbent during greater than 70 weight % (embodiment 7-cc and its next example), after compacting and between film thickness before the compacting and the ionic conductivity, little difference is arranged, promptly, can find out, although the difference of the ionic conductivity of electrolytic thin-membrane or solid electrolyte itself does not mainly depend on the content of inorganic absorbent, the influence of its content becomes big after electrolytic thin-membrane or solid electrolyte have stood pressing process.Embodiment 8 (according to the property experiment that carries out as the variation of the amount of the zeolite of inorganic absorbent)
Use zeolite to carry out in the mode identical with embodiment 7 as the experiment of inorganic absorbent.The variation of electrolytic thin-membrane and ionic conductivity is summarized in table 5 before and after the compacting.
Table 5
| Embodiment | Absorbent | ?????????PVdF | Absorbed dose (%) | Before the compacting | After the compacting | |||
| Kind | ????g | ???g | Film thickness (μ m) | Ionic conductivity (mS/cm) | Film thickness (μ m) | Ionic conductivity (mS/cm) | ||
| ????ii | Zeolite | ???0.30 | ??1.0 | ??20.5 | ????100 | ????1.8 | ????30 | ????0.10 |
| ????jj | Zeolite | ???0.44 | ??0.80 | ??35.6 | ????100 | ????2.0 | ????35 | ????0.17 |
| ????kk | Zeolite | ???0.88 | ??0.80 | ??55.1 | ????100 | ????2.0 | ????40 | ????0.26 |
| ????ll | Zeolite | ???1.42 | ??0.60 | ??70.3 | ????100 | ????1.9 | ????50 | ????0.50 |
| ????mm | Zeolite | ???1.50 | ??0.55 | ??73.2 | ????100 | ????2.0 | ????60 | ????0.75 |
| ????nn | Zeolite | ???1.50 | ??0.38 | ??79.8 | ????100 | ????2.0 | ????75 | ????1.2 |
| ????oo | Zeolite | ???2.00 | ??0.27 | ??88.1 | ????100 | ????2.2 | ????85 | ????1.8 |
| ????pp | Zeolite | ???3.99 | ??0.21 | ??95.0 | ????100 | ????2.3 | ????90 | ????2.0 |
| Zeolite | ???4.20 | ??0.13 | ??97.0 | ????100 | ????2.4 | ????90 | ????2.1 | |
Confirm, after compacting and between film thickness before the compacting and the ionic conductivity, little difference is arranged when the content of inorganic absorbent during greater than 80 weight % (embodiment 8-11 and its next example) by the result of embodiment 7.Result to embodiment 7 and present embodiment summarizes, and the correlation of the kind of above-mentioned as can be seen characteristic phenomenon and inorganic substances is little.Also can expect,, when measuring the performance of battery then, will demonstrate the tangible difference that depends on inorganic absorbent content when containing those electrolytical batteries by lamination or compacting manufacturing.Embodiment 9 (testing) according to the battery performance that the variation of inorganic absorbent kind and content is carried out
Constitute battery in the mode identical with embodiment 6, research changes the influence to battery of the kind of inorganic absorbent and content.The composition of battery and result of the test are summarized in table 6 and are shown in Figure 4 and 5.As can be seen from Table 6, each solid electrolyte all is liquid electrolyte and is absorbed into state in the electrolytic thin-membrane.
Table 6
| Embodiment | Negative electrode | Anode | Solid electrolyte | Figure | ||||||
| Active material | Conductive materials | Adhesive | Additive | Active material | Conductive materials | Adhesive | Additive | |||
| ????rr | ??LiCoO 2 | Carbon black | ??PVdF | Paragonite | Graphite | Carbon black | ??PVdF | Paragonite | Embodiment 7-(y) | Fig. 4-I |
| ????ss | ??LiCoO 2 | Carbon black | ??PVdF | Paragonite | Graphite | Carbon black | ??PVdF | Paragonite | Embodiment 7-(aa) | Fig. 4-J |
| ????tt | ??LiCoO 2 | Carbon black | ??PVdF | Paragonite | Graphite | Carbon black | ??PVdF | Paragonite | Embodiment 7-(dd) | Fig. 4-K |
| ????uu | ??LiCoO 2 | Carbon black | ??PVdF | Paragonite | Graphite | Carbon black | ??PVdF | Paragonite | Embodiment 7-(ff) | Fig. 4-L |
| ????vv | ??LiCoO 2 | Carbon black | ??PVdF | Zeolite | Graphite | Carbon black | ??PVdF | Zeolite | Embodiment 8-(ii) | Fig. 5-M |
| ????ww | ??LiCoO 2 | Carbon black | ??PVdF | Zeolite | Graphite | Carbon black | ??PVdF | Zeolite | Embodiment 8-(kk) | Fig. 5-N |
| ????xx | ??LiCoO 2 | Carbon black | ??PVdF | Zeolite | Graphite | Carbon black | ??PVdF | Zeolite | Embodiment 8-(mm) | Fig. 5-O |
| ????yy | ??LiCoO 2 | Carbon black | ??PVdF | Zeolite | Graphite | Carbon black | ??PVdF | Zeolite | Embodiment 8-(oo) | Fig. 5-P |
From above result of the test as can be seen, (embodiment 9-tt, uu or embodiment 9-xx yy) can demonstrate performance than the better off of other content in the solid electrolyte under the situation of inorganic absorbent content greater than 70 weight %.Sum up embodiment 7,8 and the result of present embodiment as can be seen, although only concerning electrolytic thin-membrane or solid electrolyte itself, it does not almost have any difference as the character of ionic conductivity, mechanical strength etc. along with the difference of inorganic absorbent content, but when manufacturing battery they are carried out lamination or when compacting, the influence of absorbent contents but shows widely.In other words, we can say, when the content of inorganic absorbent surpasses 70 weight %, even after the battery assembling, absorb the also not forfeiture of the electrolytical ability of liquid, and fabulous influence is arranged for the performance of battery.How also confirm, no matter the kind of inorganic absorbent all can show this phenomenon.
Industrial applicibility
The invention provides the solid electrolyte with good ionic conductivity, it by so that liquid electrolyte absorb at an easy rate and added inorganic absorbent and having introduced in the porous electrolytic thin-membrane and form. The present invention also provides the method for those solid electrolytes of preparation; With use this solid electrolyte as electrolytical chargeable lithium cell. The advantage of solid electrolyte of the present invention is that manufacture process and material requirements are simple, and electrolytical capacity and excellent in stability use the assembling of battery of this solid electrolyte easy. Particularly, because the inorganic absorbent that adds has surpassed specific amount, so in lamination or pressing process, can keep porous and the electrolytical ability of liquid-absorbing of electrolytic thin-membrane, also can keep with the equally good good character of solid electrolyte itself thus even after the battery assembling.
Claims (8)
1. solid electrolyte that is used for rechargeable battery comprises:
Thickness is 20-200um and has the electrolytic thin-membrane of multi-cellular structure, and wherein electrolytic thin-membrane comprises particle diameter and is no more than the inorganic absorbent that 40um, consumption surpass 70 weight % of electrolytic thin-membrane total weight under the drying condition that does not wherein contain liquid electrolyte at least; With
The liquid electrolyte of ionic conductivity, its amount is the 20-90 weight % that comprises the electrolyte total weight of liquid electrolyte.
2. the solid electrolyte that is used for rechargeable battery according to claim 1, wherein the content of inorganic absorbent is 70-95 weight %.
3. the solid electrolyte that is used for rechargeable battery according to claim 1, wherein
Described inorganic absorbent is served as reasons and is selected from the mixture of one or both or the multiple composition organized below:
Mineral grain with phyllosilicate structures is as clay, paragonite, montmorillonite and mica; The synthesis oxide compound particle is as zeolite, porous silica and Woelm Alumina, magnesium oxide; The mesoporosity molecular sieve that the aperture is 2-30um, made by oxide or polymer; And other commercially available absorbents;
Described polymer adhesive is served as reasons and is selected from the mixture of one or both or the multiple composition organized below:
Polyvinylidene fluoride, the copolymer of vinylidene fluoride and hexafluoropropylene, the copolymer of vinylidene fluoride and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethane, polysulfones, polyethers, polyethylene, polypropylene, poly(ethylene oxide), polyisobutene, polybutadiene, polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethylene glycol) diacrylate, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer or mixture.
4. according to the solid electrolyte of the rechargeable battery of claim 1, wherein said electrolytic thin-membrane prepares by wet method, described wet method comprises: inorganic absorbent is dispersed in the solution by polymer adhesive and solvent composition thereof, the gained mixture is prepared into film, with the non-solvent exchange solvent that is used for polymer adhesive, the step of dry then gained material.
5. according to the solid electrolyte of the rechargeable battery of claim 4, wherein
The described solvent that is used for polymer adhesive is served as reasons and is selected from the mixture of a kind of two or more solvent compositions of organizing below:
The N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane;
The described non-solvent that is used for polymer adhesive is served as reasons and is selected from the mixture of one or both or the multiple solvent composition organized below:
Water, ethanol, ethylene glycol, glycerine, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
6. according to any one the solid electrolyte that is used for rechargeable battery of claim 1-4, wherein
Described solid electrolyte prepares by activation process, and wherein the ionic conductivity liquid electrolyte is absorbed in the described electrolytic thin-membrane, and
Described ionic conductivity liquid electrolyte is by being selected from LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiSCN, LiCF
3SO
3, LiN (CF
3SO
2)
2And LiC (CF
3SO
2)
3One or both or multiple lithium salts to be dissolved into concentration be obtaining by being selected from the mixture that one or both or the multiple organic solvent organized below form of 0.5M-2M:
Ethylene carbonate, propylene carbonate, carbonic acid fourth diester, dimethyl carbonate, diethyl carbonate, ethylene methyl esters, r-butyrolactone, 1,3-dioxane, oxolane, 2-methyltetrahydrofuran, methyl-sulfoxide, sulfolane, N, dinethylformamide, diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether.
7. chargeable lithium cell, it obtains through the following steps:
The inorganic absorbent that particle diameter is no more than 40um is that 70/30-95/5 is distributed in the solution by polymer adhesive and solvent composition thereof with the weight ratio based on polymer adhesive,
The gained mixture is made film,
Exchange described solvent with the non-solvent that is used for polymer adhesive, and to be dried to form thickness be many micropores electrolytic thin-membrane of 20-200um, wherein micro-pore diameter is no more than 20um, and porosity is 5-95%,
The gained electrolytic thin-membrane is arranged between negative electrode and the anode,
By as lamination or pressing mode with the resulting structures lamination with in conjunction with it is assembled into the form of battery, then
Make the gained battery absorb the ionic conductivity liquid electrolyte.
8. according to the chargeable lithium cell of claim 7, wherein
Described negative electrode prepares in the mode of separating with electrolytic thin-membrane with described anode,
The polymer adhesive that is used for negative electrode and/or anode is identical or compatible with the polymer adhesive of electrolytic thin-membrane,
Be used for negative electrode and/additive of anode is one or both or the multiple mixture that is used for the electrolytic thin-membrane absorbent that is selected from.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2000/000482 WO2001099220A1 (en) | 2000-05-24 | 2000-05-24 | Microporous solid electrolytes and methods for preparing them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1452794A true CN1452794A (en) | 2003-10-29 |
Family
ID=19198207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00819535A Pending CN1452794A (en) | 2000-05-24 | 2000-05-24 | Microporous solid electrolytes and methods for preparing them |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1290749A4 (en) |
| JP (1) | JP2003536233A (en) |
| CN (1) | CN1452794A (en) |
| WO (1) | WO2001099220A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1290749A4 (en) | 2004-09-22 |
| WO2001099220A1 (en) | 2001-12-27 |
| JP2003536233A (en) | 2003-12-02 |
| EP1290749A1 (en) | 2003-03-12 |
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